Yu Fang

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

The ex vivo application of enzymes in various processes, especially via enzyme immobilization techniques, has been extensively studied in recent years in order to enhance the recyclability of enzymes, to minimize enzyme contamination in the product, and to explore novel horizons for enzymes in biomedical applications. Possessing remarkable amenability in structural design of the frameworks as well as almost unparalelled surface tunability, Metal-Organic Frameworks (MOFs) have been gaining popularity as candidates for enzyme immobilization platforms. Many MOF-enzyme composites have achieved unprecedented results, far outperforming free enzymes in many aspects. This review summarizes recent developments of MOF-enzyme composites with special emphasis on preparative techniques and the synergistic effects of enzymes and MOFs. The applications of MOF-enzyme composites, primarily in transferation, catalysis and sensing, are presented as well. The enhancement of enzymatic activity of the composites over free enzymes in biologically incompatible conditions is emphasized in many cases.

Natural enzymes catalyze reactions in their substrate-binding cavities, exhibiting high specificity and efficiency. In an effort to mimic the structure and functionality of enzymes, discrete coordination cages were designed and synthesized. These self-assembled systems have a variety of confined cavities, which have been applied to accelerate conventional reactions, perform substrate-specific reactions, and manipulate regio- and enantio-selectivity. Many coordination cages or cage-catalyst composites have achieved unprecedented results, outperforming their counterparts in different catalytic reactions. This tutorial review summarizes recent developments of coordination cages across three key approaches to coordination cage catalysis: (1) cavity promoted reactions, (2) embedding of active sites in the structure of the cage, and (3) encapsulation of catalysts within the cage. Special emphasis of the review involves (1) introduction of the structure and property of the coordination cage, (2) discussion of the catalytic pathway mediated by the cage, (3) elucidation of the structure-property relationship between the cage and the designated reaction. This work will summarize the recent progress in supramolecular catalysis and attract more researchers to pursue cavity-promoted reactions using discrete coordination cages.

Abstract Delivering sufficient water to the evaporation surface/interface is one of the most widely adopted strategies to overcome salt accumulation in solar‐driven interfacial desalination. However, water transport and heat conduction loss are positively correlated, resulting in the trade‐off between thermal localization and salt resistance. Herein, a 3D hydrogel evaporator with vertical radiant vessels is prepared to surmount the long‐standing trade‐off, thereby achieving high‐rate and stable solar desalination of high‐salinity. Experiments and numerical simulations reveal that the unique hierarchical structure, which consists of a large vertical vessel channel, radiant vessels, and porous vessel walls, facilitates strong self‐salt‐discharge and low longitudinal thermal conductivity. With the structure employed, a groundbreaking comprehensive performance, under one sun illumination, of evaporation rate as high as 3.53 kg m −2 h −1 , salinity of 20 wt%, and a continuous 8 h evaporation is achieved, which thought to be the best reported result from a salt‐free system. This work showcases the preparation method of a novel hierarchical microstructure, and also provides pivotal insights into the design of next‐generation solar evaporators of high‐efficiency and salt tolerance.

Prodrug activation, by exogenously administered enzymes, for cancer therapy is an approach to achieve better selectivity and less systemic toxicity than conventional chemotherapy. However, the short half-lives of the activating enzymes in the bloodstream has limited its success. Demonstrated here is that a tyrosinase-MOF nanoreactor activates the prodrug paracetamol in cancer cells in a long-lasting manner. By generating reactive oxygen species (ROS) and depleting glutathione (GSH), the product of the enzymatic conversion of paracetamol is toxic to drug-resistant cancer cells. Tyrosinase-MOF nanoreactors cause significant cell death in the presence of paracetamol for up to three days after being internalized by cells, while free enzymes totally lose activity in a few hours. Thus, enzyme-MOF nanocomposites are envisioned to be novel persistent platforms for various biomedical applications.